Patent GB-928417-A (GB)
Title: Steroid compounds
IPC: C07J5/00
Filed: 1959-07-08
Abstract: The invention comprises steroids of the general formulae <FORM:0928417/IV(a)/1> and <FORM:0928417/IV(a)/2> wherein R represents hydrogen or an acyl group, and Y is hydrogen or bromine; and the preparation of a 3-acyloxy (or hydroxy)-20-keto-9(11),16-pregnadiene by treating a 3-acyloxy (or hydroxy)- 17a -bromo-20-keto-9(11)-pregnene with a dehydrohalogenating agent such as a tertiary amine, lithium chloride in an N.N-di(lower alkyl) amide, or dimethyl formamide, or by treating a 3a -acyloxy (or hydroxy)- 17a ,21-dibromo-20-keto-9(11)-pregnene with an alkali metal iodide at a temperature above 40 DEG C.; the preparation of a 3a -acyloxy (or hydroxy)-17a -bromo-20-keto-9(11)-pregnene by reacting a 3a -acyloxy (or hydroxy)-11b -hydroxy-20-keto-pregnane with bromine under neutral or acid conditions at an elevated temperature at or above 25 DEG C. in an approximately equimolar ratio of the pregnane compound to bromine and by reacting a 3a -acyloxy (or hydroxy)-17a ,21-dibromo- 20-keto-9(11)-pregnene with an alkali metal iodide at a temperature below 35 DEG C. to form a 3a -acyloxy (or hydroxy)- 17a -bromo- 21-iodo- 20-keto-9(11)-pregnene and replacing the 21-iodine atom in this compound by a hydrogen atom, for example, by means of an alkali metal bisulphite; a process for the preparation of a 3a -acyloxy (or hydroxy)-17a ,21-dibromo-20-keto-9(11)-pregnene by reacting a 3a -acyloxy (or hydroxy)-11b -hydroxy- 20-keto-pregnane with bromine under neutral or acid conditions at an elevated temperature above 25 DEG C. in a ratio of 1 mole of the pregnane compound to approximately 2 moles of bromine and by heating a 3a -acyloxy (or hydroxy)-11b -hydroxy-17a ,21-dibromo- 20-keto-pregnane in contact with a strong acid catalyst such as hydrobromic acid, p-toluenesulphonic acid or 3,5-dinitro-benzenesulphonic acid; a process for the preparation of a 3a -acyloxy (or hydroxy)-11b -hydroxy- 17a ,21-dibromo-20-keto-pregnane by reacting 3a -acyloxy (or hydroxy)-11b -hydroxy-20-keto-pregnane with bromine in a ratio of 1 mole of the pregnane compound to approximately 2 moles of bromine at a temperature below 25 DEG C. or in the presence of a Lewis base such as methanol; a process for the preparation of a 3a -acyloxy (or hydroxy)-11b -hydroxy-20-keto-16-pregnene by treating 3a -acyloxy (or hydroxy)-11b -hydroxy-17a -bromo- 20-keto-pregnane with a dehydrohalogenating agent such as a tertiary amine, lithium chloride in an N,N-di(lower alkyl) amide or dimethylformamide, or by treating 3a -acyloxy (or hydroxy)-11b -hydroxy-17a ,21-dibromo- 20-ketopregnane with an alkali metal iodide at a temperature above 40 DEG C.; and a process for the preparation of 3a -acyloxy (or hydroxy)-11b -hydroxy-17a -bromo-20-keto-pregnane by reacting 3a -acyloxy (or hydroxy)- 11b -hydroxy-17a ,21-dibromo-20-ketopregnane with an alkali metal iodide at a temperature of less than 35 DEG C. to form a 3a -acyloxy (or hydroxy-11b -hydroxy-17a -bromo-20-keto-21-iodopregnane and replacing the 21-iodine atom by a hydrogen atom, or by reacting a 3a -acyloxy (or hydroxy)- 11b -hydroxy- 20-ketopregane with an approximately equimolar amount of bromine at a temperature below 25 DEG C. in the presence of a Lewis base.